Process and Device for Chlorine-Free Shrinkproof Treatment of Wool Raw Material and Article Thereof

ABSTRACT

The present invention relates to a process and a device for chlorine-free shrinkproof treatment of a wool raw material and an article thereof. In particular, the process of the present invention comprises the steps of a chlorine-free shrinkproof treatment, washing with water, protease inactivation, a softening treatment, dehydration, drying and the like, wherein a chlorine-free catalysis system consisting of a protease, a specific organic phosphine compound and the like is selected, removing the scale layer on the surface of wool fibres cooperatively and efficiently and modifying the scale layer so as to improve the shrinkproof performance of wool articles. The process of the present invention can completely replace the chloridisation shrinkproof method in the prior art, and is not only environmentally friendly, but also has low requirements for equipment, can be operated continuously and is suitable for large-scale industrial production.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to wool product processing field, andparticularly, to a process and device for chlorine-free shrinkprooftreatment of wool raw material and article thereof, and moreparticularly to a chlorine-free continuous processing process and devicefor shrinkproof treatment of wool and wool article.

Description of Related Art

Wool is an important raw material of textile industry and has manyexcellent characteristics, such as good elasticity, stronghygroscopicity, not easy to stain, good warmth retention and softluster. Wool, as a natural protein fiber, has a scale layer attachedonto the surface thereof which is mainly composed of keratin andoverlapped with each other as fish scales. Due to different frictioncoefficients along scale direction and against scale direction, underrepeated external force, wool fibers will intersperse, entangle, wrapand felt with each other, thereby producing fulling. Although fullingmakes wool fabric have effects such as beautiful appearance, rich andsoft feel, and good warmth retention, it also makes wool fabric prone tosize shrinkage and deformation in a washing process. Therefore, in orderto improve shrinkproof properties of wool textile, surface modificationtreatment of wool fiber scale is necessary from the beginning so thatthe dimensional stability of wool fabric product is improved and theproduct can achieve “machine washable” effect.

At present, the main modification shrinkproof treatment methods of woolsurface scale include: chlorination method, covering method, proteasemethod and so on. The most extensive method is chlorination shrinkprooftreatment method. However, organic halide AOX (which is absorbableorganic halide) generated during the chlorination process will seriouslypollute environment.

Chinese patent CN201010605809.9 has reported a shrinkproofscale-stripping process in which potassium permanganate and DCCA as acatalyst are added into water, and then chlorine gas is passed into soas to conduct a shrinkproof scale-stripping for wool tops. This methodreduces 30% of chlorine usage on the basis of the original chlorineusage. Although this method has improved traditional chlorinationmethod, but it still uses chlorine gas and causes serious environmentalpollution. The covering method makes the wool surface scale voids filledby depositing a layer of resin film on surface of wool so as to makewool surface become smooth, thereby reducing surface friction effect offibers. Although this treatment method can improve felting performanceof fibers to a certain extent, it seriously affects the touching feel ofwool fabric and has a shortage of poor durability. Protease method makesthe scales and cell membrane complex etc. of wool partially dissolved byusing protease hydrolysis of peptide bonds of macromolecules on woolfiber surface, so as to partially or totally remove the scales. Thistreatment method has advantages such as mild handling conditions, energyconservation and pollution reduction etc., and is an environmentallyfriendly wool shrinkproof treatment method. However, the shrinkproofeffect obtained by using protease alone to treat wool is still unable tomeet the actual requirements at present, so when protease is used forbiological modification treatment of wool, in many cases, the woolfirstly needs pretreatment (such as preoxidation by using strongoxidants such as potassium permanganate etc., or pretreatment by using achloride solvent). The above-mentioned pretreatment methods havedisadvantages such as the treatment time is too long, the enzyme is easyto inactivate, the treatment condition is difficult to control and soon.

In addition, although researchers have attempted to developchlorine-free shrinkproof treatment processes for wool raw materials,those processes have the following disadvantages: (a) the treatment timeis long (The time cannot be shortened into 30 minutes or less ifprocessing quality should be ensured); (b) the treatment capacity islimited and unsuitable for industrial applications; (c) the treatmentquality is of high volatility and it is difficult to obtain woolprocessing products with uniform processing effect. Therefore, in majorwool raw materials processing countries such as China, at present, nowool raw materials are processed with a chlorine-free shrinkprooftreatment process in actual production.

In summary, there is an urgent need in the art to develop a woolshrinkproof treatment process which is environmentally friendly, simpleand easy to control, of long-lasting anti-felting effect, of high (orfast) treatment efficiency and suitable for mass production.

BRIEF SUMMARY OF THE INVENTION

The object of the present invention is to provide a wool shrinkprooftreatment process which is environmentally friendly, simple and easy tocontrol, of long-lasting anti-felting effect, of high (or fast)treatment efficiency and suitable for mass production.

In the first aspect of the present invention, a shrinkproof treatmentagent for chlorine-free shrinkproof treatment is provided, and theshrinkproof treatment agent comprises: (a) an optional solvent; (b) aprotease; and (c) an organic phosphine compound represented by formulaA; and an optional inorganic salt:

P—(X)₃  A

wherein each X is independently selected from the group consisting ofsubstituted or unsubstituted C₁-C₁₀ hydrocarbyl, wherein the term“substituted” refers to one or more substituents selected from the groupconsisting of —OH, —COOH (carboxy), C₂-C₈ ester group, —SH, —CN, C₁-C₃alkyl, and C₁-C₃ alkoxy;and at least one X is a substituted C₁-C₁₀ hydrocarbyl having a —OH orCOOH substituent; the weight ratio of the protease to the organicphosphine compound is (0.2 to 10):(0.5 to 20);and the protease in the shrinkproof treatment agent is selected from thegroup consisting of a neutral protease, an alkaline protease, andcombinations thereof.

In another preferred embodiment, the chlorine-free treatment comprisesdescaling/shrinkproof treatment for a wool raw material and/or a woolproduct.

In another preferred embodiment, the wool raw material comprises wooltop.

In another preferred embodiment, the weight ratio of the protease to theorganic phosphine compound is (0.5 to 5):(1 to 10); and more preferably(1 to 5):(1 to 10).

In another preferred embodiment, the shrinkproof treatment agent furthercomprises a basic compound. Preferably, the basic compound is selectedfrom the group consisting of alkali metal hydroxides, alkaline earthmetal hydroxides, alkali metal carbonates, alkaline earth metalcarbonates, alkali metal bicarbonates, alkaline earth metal bicarbonate,and combinations thereof.

In another preferred embodiment, the basic compound is selected from thegroup consisting of NaOH, KOH, Ca(OH)₂, Na₂CO₃, K₂CO₃, and combinationsthereof.

In another preferred embodiment, the “chlorine-free” means that theshrinkproof treatment agent does not contain an organochlorine compoundand does not include a hypochlorous compound selected from the groupconsisting of: a compound containing ClO⁻ ion (root) and a compoundwhich can produce ClO⁻ ion (such as chlorine gas).

In another preferred embodiment, in the shrinkproof treatment agent, thecontent of the hypochlorous compound is ≦0.05% by weight, preferably≦0.01% by weight, more preferably ≦0.001% by weight, and most preferablyabout 0. In another preferred embodiment, the shrinkproof treatmentagent is a liquid (i.e., a treatment solution).

In another preferred embodiment, the solvent is selected from the groupconsisting of water or an aqueous solvent.

In another preferred embodiment, the shrinkproof treatment agent is asolid or semi-solid, and can be reconstituted into a treatment solutionby adding a solvent (e.g., water) upon application.

In another preferred embodiment, in the treatment solution (or thereconstituted treatment solution), the concentration of the organicphosphine compound is from 1 to 10 g/L, preferably from 1.5 to 10 g/L,and more preferably from 5 to 10 g/L.

In another preferred embodiment, in the treatment solution (or thereconstituted treatment solution), the concentration of the protease is0.1 to 25 g/L, preferably 0.2 to 10 g/L, and more preferably 0.5 to 5g/L.

In another preferred embodiment, in the treatment solution (or thereconstituted treatment solution), the concentration of the inorganicsalt is 0.01 to 10 g/L, preferably 0.05 to 5 g/L, and more preferably0.1 to 2 g/L.

In another preferred embodiment, two X are identical.

In another preferred embodiment, three X are identical.

In another preferred embodiment, three X are different from each other.

In another preferred embodiment, each X is independently selected fromthe group consisting of substituted or unsubstituted C1-C6 hydrocarbyl.

In another preferred embodiment, the C1-C10 hydrocarbyl includes C1-C10alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C3-C8 cycloalkyl.

In another preferred embodiment, the C1-C10 hydrocarbyl includes C1-C10alkyl and C3-C8 cycloalkyl.

In another preferred embodiment, when the shrinkproof treatment agentcontains one or more components selected from the group consisting of aprotease, an organic phosphine compound, an inorganic salt, and asurfactant, the contents thereof are as follows:

Preferred More Preferred Component Content content Content Protease 0.01to 2.5 wt % 0.02 to 1.0 wt % 0.05 to 0.5 wt % (or 0.1 to 25 g/L) (or 0.2to 10 g/L) (or 0.5 to 5 g/L) organic 0.01 to 5.0 wt % 0.05 to 2.0 wt %0.1 to 1.0 wt % phosphine or 0.1 to 50 g/L or 0.5 to 20 g/L or 1 to 10g/L compound inorganic salt 0.001 to 1.0 wt % 0.005 to 0.5 wt % 0.01 to0.2 wt % or 0.01 to 10 g/L 0.05 to 5g/L 0.1 to 2 g/L Surfactant 0.001 to1.0 wt % 0.005 to 0.5 wt % 0.01 to 0.2 wt % or 0.01 to 10 g/L 0.05 to 5g/L 0.1 to 2 g/L

In another preferred embodiment, in the shrinkproof treatment agent, theamount (wt) of the protease is less than or equal to (≦) the amount (wt)of the organic phosphine compound.

In another preferred embodiment, when the shrinkproof treatment agent isan aqueous solution or a reconstituted aqueous solution, pH thereof isfrom 6.5 to 12, preferably from 7 to 11.5, and more preferably from 7.5to 10.5. In another preferred embodiment, the protease is an alkalineprotease.

In another preferred embodiment, the organic phosphine compound is awater-soluble aliphatic organic phosphine compound.

In another preferred embodiment, the water-soluble refers to solubilityof the organic phosphine compound in 100 g of water at 25° C. is ≧0.1 g,preferably ≧0.5 g, and more preferably ≧2 g, such as 0.1 to 10 g or 0.5to 5 g.

In another preferred embodiment, the organic phosphine compound has thefollowing structure formula:

P—(R₁-R₂)₃  I

wherein, R₁ is substituted or unsubstituted C₂-C₈ alkylene (preferablyC₁-C₆ alkylene); and/or R₂ is selected from the group consisting of —OH,—COOH, C₂-C₈ ester group, alkali metal, and alkaline earth metal.

In another preferred embodiment, in the compound of formula I, R₁ isunsubstituted C₁-C₆ alkylene; and/or R₂ is selected from the groupconsisting of —OH and —COOH.

In another preferred embodiment, R₁ is selected from the groupconsisting of methylene, ethylene, propylene, butylene, pentylene,hexylene, and combinations thereof.

In another preferred embodiment, the aliphatic organic phosphinecompound is selected from the group consisting oftris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine,tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, andcombinations thereof.

In another preferred embodiment, the inorganic salt is selected from thegroup consisting of Ca salts, Mg salts, Na salts, Zn salts, Al salts, Basalts, and combinations thereof.

In another preferred embodiment, the inorganic salt is selected from thegroup consisting of hydrochlorate, sulfate, carbonate, bicarbonate,nitrate, nitrite, phosphate, monohydrogen phosphate, dihydrogenphosphate, and combinations thereof.

In another preferred embodiment, the inorganic salt is selected from thegroup consisting of Mg(NO₃)₂, sodium phosphate, calcium hydrogenphosphate, CaCl₂, and combinations thereof.

In another preferred embodiment, the surfactant is selected from thegroup consisting of nonionic surfactants, anionic surfactants, cationicsurfactants, amphoteric surfactants, and combinations thereof.

In another preferred embodiment, the shrinkproof treatment agent furthercomprises a pH buffer. In another preferred embodiment, the amount ofthe pH buffer is from 0.1 to 10 g/L, and preferably from 0.2 to 5 g/L.

In another preferred embodiment, the pH buffer is selected from thegroup consisting of disodium hydrogen phosphate-sodium dihydrogenphosphate buffer (PBS), NaHCO₃—Na₂CO₃ buffer, and combinations thereof.

In another preferred embodiment, the shrinkproof treatment agent isliquid at 25 to 80° C.

In another preferred embodiment, the shrinkproof treatment agent isliquid at an application temperature of from 30 to 70° C., preferablyfrom 40 to 60° C., and more preferably from 45 to 55° C.

In another preferred embodiment, in the chlorine-free treatment, thesize of wool tops to be treated is 10-30 g/m/piece, and preferably 20 to25 g/m/piece.

In another preferred embodiment, in the chlorine-free treatment, npieces of wool tops are treated in parallel and simultaneously, whereinn is from 10 to 100, from 20 to 70, and preferably from 30 to 60. In thesecond aspect of the present invention, a shrinkproof treatment devicefor chlorine-free wool tops or wool products is provided, whichcomprises:

a multiple padding apparatus which comprises n independent, continuouslyarranged padding machines, and every padding machine comprises a soakingtank and a rolling roller, wherein the soaking tank is used for placinga shrinkproof treatment agent for chlorine-free shrinkage treatment andthe wool tops or the wool products to be treated are immersed in thetreatment agent; and the rolling roller is used for rolling soaked wooltops or wool product, and the wool tops or wool product rolled byrolling rollers upstream enters into the soaking tank and the rollingroller of the padding machine downstream in turn, thereby repeating thesoaking and rolling treatment, wherein n is a positive integer of 2 to20;

a water washing apparatus for water washing the padded wool tops or woolproducts to form washed wool tops or wool products;

an enzyme inactivation apparatus for alkaline inactivation treatment ofresidual protease in the washed wool tops or wool products to form anenzyme-inactivated wool tops or wool products;

an optional soft processing apparatus for soft processing theenzyme-inactivated wool tops or wool products to form a softened wooltops or wool products; and an optional dryer used to dry the softenedwool tops or wool products obtained in the previous step.

In the third aspect of the present invention, it provides achlorine-free shrinkproof treatment method for wool tops or woolproducts, which comprises the following steps:

(a) providing chlorine-free wool tops or wool products to be treated,and a shrinkproof treatment agent for chlorine-free wool tops or woolproducts according to the first aspect of the present invention;

(b) padding the chlorine-free wool tops or wool products to be treatedwith the shrinkproof treatment agent for n times, thereby obtainingpadded wool products, wherein n is a positive integer of 2 to 20;

(c) water washing the padded chlorine-free wool tops or wool products,thereby obtaining water washed chlorine-free wool tops or wool products;and

(d) conducting an enzyme inactivation treatment of the water washedchlorine-free wool tops or wool products, thereby obtaining shrinkprooftreated chlorine-free wool tops or wool products.

In another preferred embodiment, n is a positive integer of 3 to 10. Inanother preferred embodiment, during and/or after the padding treatmentfor n times, a treatment agent containing only the protease but not theorganic phosphine compound may be additionally used to treat.

In another preferred embodiment, total time T of the padding treatmentof step (b) is ≦15 minutes, preferably ≦10 minutes, more preferably ≦5minutes, and most preferably ≦3 minutes.

In another preferred embodiment, the chlorine-free wool tops or woolproducts to be treated in step (a) is flattened.

In another preferred embodiment, the wool tops has a component selectedfrom the group consisting of wool, cashmere, and a combination thereof.

In another preferred embodiment, the wool tops has a size of 40 to 150branches, preferably 40 to 120 branches, and more preferably 56 to 100branches.

In another preferred embodiment, in step (b), the temperature for thepadding treatment is 5 to 80° C., preferably 10 to 60° C., morepreferably 25 to 50° C., and most preferably 40 to 50° C.

In another preferred embodiment, in step (b), total time for the paddingtreatment is not particularly limited, and is usually 1 to 20 minutes,preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

In another preferred embodiment, in step (c), the temperature for thewater washing is not particularly limited and is usually from 5 to 60°C., preferably from 10 to 50° C., more preferably from 20 to 40° C., andmost preferably from 20 to 30° C.

In another preferred embodiment, in step (c), time for the water washingis not particularly limited and is usually 30 seconds to 120 minutes,preferably 1 minute to 60 minutes, and more preferably 2 to 30 minutes.

In another preferred embodiment, the enzyme inactivation treatment usesconventional inactivation conditions as long as the residual protease isinactivated or substantially inactivated.

In another preferred embodiment, no hypochlorous compound is used in themethod.

In another preferred embodiment, in step (b), ratio of the volume of theshrinkproof treatment agent to the weight of the wool products to betreated is not particularly limited as long as the wool tops or woolproducts to be treated can be wetted.

In another preferred embodiment, in step (b), times of the padding maybe the same or different, and preferably the same.

In another preferred embodiment, in step (b), the times of the paddingis 3 to 15 times, preferably 4 to 12 times, and more preferably 5 to 10times.

In another preferred embodiment, treatment time of the padding in step(b) is 3 to 1000 s, preferably 5 to 800 s, more preferably 8 to 600 s,and most preferably 10 to 300 s.

In another preferred embodiment, the padded wool products obtained instep (b) has a liquid-containing rate of 50 to 160 wt %, preferably 60to 150 wt %, and more preferably 80 to 140 wt %.

In another preferred embodiment, before step (c), step (b) is repeated,and repetition times is 3 to 15 times, preferably 4 to 12 times, andmore preferably 5 to 10 times.

In another preferred embodiment, before repeating step (b) for everytime, it further comprises a step of replacing the shrinkproof treatmentagent.

In another preferred embodiment, in step (c), the temperature of waterused for the water washing is 10-40° C., and preferably 20 to 30° C.

In another preferred embodiment, pH of water used for the water washingis 6.5-7.5, preferably 7. In another preferred embodiment, in step (c),the padded wool products obtained in step (b) is water washed with acertain amount of water.

In another preferred embodiment, in step (c), the water washing isconducted 1 to 6 times, preferably 2 to 4 times.

In another preferred embodiment, the time for the water washing in step(c) is 1 to 60 minutes, preferably 1 to 30 minutes, and more preferably1 to 10 minutes.

In another preferred embodiment, before step (d), step (c) is repeatedand repetition times are 1 to 6 times, preferably 2 to 4 times.

In another preferred embodiment, in step (d), the inactivation treatmentis carried out by using a method selected from the group consisting ofhot water inactivation, hydrogen peroxide (H₂O₂) inactivation, andcombination thereof.

In another preferred embodiment, the temperature of hot water used inthe hot water inactivation is 85 to 100° C., preferably 90 to 98° C.,and more preferably 92 to 96° C.

In another preferred embodiment, treatment time of the hot waterinactivation is from 5 to 300 s, preferably from 8 to 200 s, morepreferably from 10 to 100 s.

In another preferred embodiment, in step (d), treatment time of thehydrogen peroxide inactivation treatment is from 5 to 300 s, preferablyfrom 8 to 200 s, and more preferably from 10 to 100 s.

In another preferred embodiment, after step (d), it optionally furthercomprises following steps:

5) soft processing the product obtained in step (d), thereby obtaining adesired wool product; and

6) optionally dewatering and/or drying the product obtained in theprevious step, thereby obtaining a desired wool product.

In another preferred embodiment, the soft treatment in step 5) is tosoak the product obtained in step (d) with a soft treatment agent.

In another preferred embodiment, in step 5), a ratio of the productobtained in step (d) to the soft treatment agent is a conventionalratio.

In another preferred embodiment, the soft treatment in step 5) has asoaking time in the treatment agent of 5 to 200 s, preferably 8 to 100s, and more preferably 10 to 50 s.

In another preferred embodiment, the soft treatment in step 5) has afrequency of 1 to 10 times, preferably 2 to 5 times, and more preferably3 to 4 times.

In another preferred embodiment, the treatment agent employed in thesoft treatment in step 5) has a temperature of from 25 to 65° C., andpreferably from 30 to 50° C.

In another preferred embodiment, pH of the treatment agent employed inthe soft treatment in step 5) is from 5 to 8, and preferably from 5.5 to7.5.

In another preferred embodiment, concentration of the treatment agentused in the soft treatment in step 5) is from 5 to 100 g/L, preferablyfrom 10 to 50 g/L, and more preferably from 15 to 30 g/L.

In another preferred embodiment, the treatment agent used in the softtreatment in step 5) is selected from the group consisting of woolsmoothing agents, wool softening agents, and combinations thereof.

In another preferred embodiment, treatment temperature for the dryingtreatment in step 6) is 60 to 100° C., preferably 70 to 90° C.

In another preferred embodiment, in step 6), drying treatment time atthe treatment temperature is from 1 to 30 minutes, and preferably from 3to 15 minutes.

In the fourth aspect of the present invention, it provides a shrinkproofchlorine-free wool product in which there is no residual organicchlorine.

In another preferred embodiment, the wool product is shrinkproof treatedby the shrinkproof treatment process (method) of the present invention.

In another preferred embodiment, the wool product is shrinkproof treatedwith the shrinkproof treatment agent for chlorine-free wool tops or woolproducts according to the first aspect of the present invention.

In another preferred embodiment, the wool product is chlorine-freetreated by using the shrinkproof treatment device according to thesecond aspect of the present invention.

In another preferred embodiment, after treated by the shrinkprooftreatment method, a scale layer removal rate of wool surface layer ofthe treated chlorine-free wool product is 80 to 100%, preferably from 90to 100%, more preferably from 95 to 100%, such as from 99 to 100%, whenit is compared with that of the wool product to be treated.

In another preferred embodiment, after treated by the shrinkprooftreatment method, the absolute value of shrinkage rate of the treatedchlorine-free wool product is ≦10%, preferably ≦8%, preferably ≦6%, morepreferably ≦5%, and most preferably ≦3% when it is compared with that ofthe wool product to be treated, wherein measurement method thereof isTWC.TM31 test method of the International Wool Bureau.

In another preferred embodiment, after treated by the shrinkprooftreatment method, the strength retention of the treated chlorine-freewool product is ≧80%, preferably ≧82%, more preferably ≧84% when it iscompared with that of the wool product to be treated.

In another preferred embodiment, after treated by the shrinkprooftreatment method, the elongation retention of the treated chlorine-freewool product is ≧70%, preferably ≧75%, and more preferably ≧80% when itis compared with that of the wool product to be treated.

In another preferred embodiment, the drip diffusion time of the treatedchlorine-free wool product is ≦30 s, preferably ≦15 s, and morepreferably ≦10 s.

In the fifth aspect of the present invention, an article is provided,and the article comprises the wool product or is made up of the woolproduct according to the fourth aspect of the present invention.

In another preferred embodiment, the article comprises a wool tops, awool blanket and a garment.

In the sixth aspect of the present invention, it provides a use of theshrinkproof treatment agent according to the first aspect of the presentinvention in the chlorine-free shrinkproof treatment of a wool top or awool product.

In the seventh aspect of the present invention, a shrinkproof treatmentagent for chlorine-free wool tops and wool products is provided, andmain components thereof comprises: a protease, a water-soluble aliphatictrisubstituted organic phosphine compound, and an inorganic salt,wherein the water-soluble aliphatic trisubstituted organic phosphinecompound has a structure of P—(R—S)₃, wherein R is hydrocarbylcontaining 1 to 6 carbon, S is hydroxyl or carboxyl and derivativesthereof; and mass concentration thereof is 1 to 10 g/L; the inorganicsalt is calcium chloride, and has a concentration of 0 to 2 g/L.

In another preferred embodiment, the trisubstituted organic phosphinecompound is at least one of tris(3-hydroxypropyl)phosphine,tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine andtris(4-carboxybutyl) phosphine.

In the eighth aspect of the present invention, a continuous processingprocess of shrinkproof treatment of chlorine-free wool tops and woolproducts is provided, which comprises the following steps:

1) shrinkproof treatment: wool tops and wool products are arranged, anduniformly transported with a roller (or rollers) into a number of tanksfilled with shrinkproof treatment agent and subjected to an alternatesoaking and rolling treatment for 3 to 10 times, wherein processconditions comprise: pH of the shrinkproof treatment agent is 7 to 10.5,temperature is 40 to 50° C.; a rolling liquid-containing rate is 60% to150%; process delivery speed is 3 to 15 m/min, and total time of soakingand rolling is 1 to 5 minutes;

2) water washing: the treated wool tops obtained in the previous stepare transported by rolling into one to four water tanks for multiplewashing, thereby removing residual biological enzyme activator andenzyme preparation to prevent them from continuously eroding wool;

3) inactivation of protease: the washed wool tops are evenly and quicklypassed through a hot water tank filled with hot water having atemperature of 85 to 95° C. or a solution containing 0 to 1 g/L ofhydrogen peroxide, thereby inactivating any protease which is notcompletely washed out;

4) soft treatment: the inactivated wool tops are soaked into a tankfilled with a conventional wool smoothing agent or organosiliconsoftening-agent, and a common soft treatment is conducted to improvefeel of wool fabric;

5) dehydration and drying;

wherein the shrinkproof treatment agent mainly contains: trisubstitutedorganic phosphine, with a concentration is 1 to 10 g/L; calciumchloride, with a concentration is 0.3 to 2 g/L; protease, with aconcentration is 0.5 to 5 g/L; and the rest is water; wherein thetrisubstituted organic phosphine is at least one oftris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine,tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine.

In another preferred embodiment, the soaking and rolling (or extruding)treatment is repeated for 3 to 10 times; total time for the paddingtreatment is 1-5 minutes; and process delivery speed is 3 to 8 m/min.

In another preferred embodiment, the wool tops are wool or cashmere of56 to 100 branches.

It should be understood that in the present invention, any of thetechnical features specifically described above and below (such as inthe Examples) can be combined with each other, thereby constituting newor preferred technical solutions which will not redundantly be describedone by one herein.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is an effect graph of wool fiber after scales are stripped inExample 1 of the present invention.

FIG. 2 is an effect graph of wool fiber after scales are stripped inExample 2 of the present invention.

FIG. 3 is an effect graph of wool fiber after scales are stripped inExample 3 of the present invention.

FIG. 4 is an effect graph of wool fiber after scales are stripped inExample 4 of the present invention.

FIG. 5 is an effect graph of wool fiber after scales are stripped inExample 5 of the present invention.

FIG. 6 is a flow chart of a process example of the present invention.

FIG. 7 is a schematic diagram of a chlorine-free treatment device of thepresent invention.

DETAILED DESCRIPTION OF INVENTION

Through extensive and intensive long research, the inventors haveunexpectedly prepared a descaling shrinkproof process and acorresponding shrinkproof treatment agent and a device for chlorine-freewool tops and wool products. The process and the shrinkproof treatmentagent of the invention can efficiently and rapidly remove the scalelayer on the surface of the wool fiber under chlorine-free condition andmodify the scale layer, thereby improving felting property of the woolproduct and dimensional stability of product. On this basis, theinventors have completed the present invention.

Specially, a continuous processing process of shrinkproof treatment ofchlorine-free wool tops and wool products is provided in the invention.It comprises shrinkproof treatment, water washing, proteaseinactivation, soft treatment, dehydration and drying steps.

According to a characteristic that the wool fiber is a protein fiber, ahighly efficient integrated catalytic system composed of a protease, anactivator of a water-soluble aliphatic trisubstituted organic phosphinestructure, a metal salt and non-ionic surfactant is selected, which cansynergistically and efficiently remove the scale layer on the surface ofwool fiber and modify the scale layer, thereby improving feltingproperty of the wool product and dimensional stability of product andconferring the fabric with anti-pilling characteristics and smooth feel.The invention can completely replace the chlorination shrinkproof methodin the art, and avoid the environmental pollution caused by thechlorination method. The present invention is a cleaning treatmentprocess which meets the environmental requirements, and has no problemof chlorination pollution. The method has following advantages such as:reagent usage amount is small, the cost is low, the process is simple,the requirement for equipment is low, it can be continuously conducted,and it can realize industrial production.

Terms

As used herein, the term “wool raw material” includes wool, wool top, orsemi-finished products thereof without subjecting to a descalingshrinkproof treatment. In addition, the term may also include wool rawmaterial which has been subjected to descaling shrinkproof treatment,but has not completely been descaled.

As used herein, the terms “wool top/wool product” and “wool top and/orwool product” can be used interchangeably and refer to wool top, or woolproduct, or a combination thereof. The term may include both the wooltop/wool product to be treated and the treated or being treated wooltop/wool product.

As used herein, the terms “chlorine-free product of the presentinvention” and “chlorine-free wool top/wool article of the presentinvention” can be used interchangeably and refer to the wool top/woolproduct obtained by the chlorine-free descaling shrinkproof treatmentprocess of the present invention. Since the chlorine-free descalingshrinkproof treatment process of the present invention does not use anyorganochlorine compound and does not use any hypochlorous compound(i.e., a compound containing ClO⁻ ion or a compound capable of producingClO⁻ ion), the chlorine-free wool products (including wool tops/woolproducts) have excellent safety.

As used herein, the terms “shrinkproof agent (or liquid) of the presentinvention”, “descaling shrinkproof agent (or liquid) of the presentinvention”, “the chlorine-free shrinkproof treatment agent (or liquid)”and “the chlorine-free descaling shrinkproof treatment agent (orliquid)” can be used interchangeably and refer to the shrinkprooftreatment agent (or liquid) for the chlorine-free wool top/wool productin the present invention.

Shrinkproof Treatment Agent for Chlorine-Free Wool Top/Wool Product

A descaling shrinkproof treatment agent for the chlorine-free wooltop/wool product of the present invention is provided in the presentinvention. The descaling shrinkproof treatment agent of the presentinvention may be solid or liquid. When the chlorine-free shrinkproofagent of the present invention is solid, it can be reconstituted into acorresponding shrinkproof treatment liquid used for a chlorine-free wooltop/wool product by adding water (or an aqueous solvent).

In addition, in the present invention, every combination may have beenmixed together (i.e. in a mixed form), or the components of the agentmay also be present in an unmixed form and are mixed into a formulationin situ when one need to use such agent.

In a preferred embodiment, main components of a shrinkproof treatmentliquid for chlorine-free wool top and wool product comprise a protease,a water-soluble aliphatic trisubstituted organic phosphine compound, andan inorganic salt. The structure of the water-soluble aliphatictrisubstituted organic phosphine is P—(R—S)₃, wherein R is hydrocarbylcontaining 1 to 6 carbons, S is hydroxyl or carboxyl and derivativesthereof; and mass concentration thereof is 1 to 10 g/L. The inorganicsalt is calcium chloride, and the concentration thereof is 0 to 2 g/L.

In the present invention, the preferred trisubstituted organic phosphineincludes (but is not limited to): tris(3-hydroxypropyl)phosphine,tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine,tris(4-carboxybutyl)phosphine, or combinations thereof.

In another preferred embodiment, the protease includes a neutralprotease, an alkaline protease, or a combination thereof.

In another preferred embodiment, the neutral protease refers to aprotease whose optimal pH is neutral (e.g. about 6.8 to 7.0), andmolecular weight thereof is generally from 35 to 40 kD. Neutralproteases suitable for use in the present invention include neutralproteases that are commercially available or prepared by conventionalmethods, such as neutral proteases from microorganisms, Neutrase, orcombinations thereof.

In another preferred embodiment, the alkaline protease refers to aprotease whose optimal pH is alkaline (e.g. about 9 to 11), andmolecular weight thereof is generally from 26 to 34 kD. Alkalineproteases suitable for use in the present invention include alkalineproteases that are commercially available or prepared by conventionalmethods, such as alkaline proteases from Bacillus licheniformis (aprotease belong to serine-type endoprotease and having a molecularweight of about 27300), alkaline proteases from Streptonmycetes, 2709alkaline protease, Novo protease, Carsberg protease and the like.

In the shrinkproof agent of the present invention, the concentration ofprotease is generally 0.1 to 25 g/L, preferably 0.2 to 10 g/L, and morepreferably 0.5 to 5 g/L.

According to international units (IU), the amount (or concentration) ofprotease is generally 1×10⁴-1×10⁸ U/L, preferably 5×10⁴-5×10⁷ U/L, andmore preferably 1×10⁵-1×10⁷ U/L.

In another preferred embodiment, the shrinkproof treatment liquid of thepresent invention further comprises a nonionic surfactant (e.g. JFC) oran anionic surfactant. Representative non-ionic surfactants include (butare not limited to): polyoxyethylene type surfactants such asalkylphenol polyoxyethylene ether (APEO), fatty acid polyoxyethyleneesters (AE), fatty acid methyl ester ethoxylates (FMEE), and polyol typesurfactants (such as sorbitan esters, including Tween and Span), orcombinations thereof. Representative examples include Tween, Span, JFC,or combinations thereof. Representative anionic surfactants include (butare not limited to): sodium dodecylbenzenesulfonate, sodium dodecylsulfate (SDS), hexadecylsulfonate, or combinations thereof.

In general, the concentration of surfactant is 0.001 to 1.0 wt % or 0.01to 10 g/L, and preferably 0.1 to 2 g/L.

Preferably, the pH of the shrinkproof treatment liquid of the presentinvention is from 7 to 10.5.

In another preferred embodiment, a shrinkproof treatment liquid forchlorine-free wool tops and wool products is provided in the presentinvention, which has main components in mass as follows: trisubstitutedorganic phosphine, with a concentration of 1 to 10 g/L; calciumchloride, with a concentration of 0 to 2 g/L; protease, with aconcentration of 0.5 to 5 g/L; and the rest is water.

The shrinkproof treatment agent (liquid) of the present invention candirectly treat the wool top/wool product to obtain a descalingshrinkproof wool top/wool product.

Compared with the chlorine-containing shrinkproof treatment solution inthe prior art, the shrinkproof treatment liquid of the present inventioncontains neither an organochlorine compound nor a hypochlorous compound(i.e., a compound containing ClO⁻ ion or a compound capable of producingClO⁻ ion such as Cl₂). The organochlorine compounds include DCCA,chloroform, carbon tetrachloride, TCCA and the like.

In another preferred embodiment, the main components of the shrinkprooftreatment liquid of the chlorine-free wool top and wool product of thepresent invention are protease, water-soluble aliphatic trisubstitutedorganic phosphine compound and inorganic salt.

In which, the water-soluble aliphatic trisubstituted organic phosphinehas a structure of P—(R—S)₃, wherein R is a hydrocarbyl having 1 to 6carbon (C), and S is hydroxyl (—OH) or carboxyl (—COOH) and derivativesthereof. The usage amount is 1 g˜10 g/L. The inorganic salts are calciumchloride etc., and usage amount thereof is 0 g/L˜2 g/L.

The trisubstituted organic phosphine is at least one oftris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine,tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine.

The protease is a neutral protease, an alkaline protease and the like,and the concentration of protease is 0.5 g/L to 5 g/L.

The pH of the shrinkproof treatment liquid is 7 to 10.5.

In another preferred embodiment, the main components of the shrinkprooftreatment liquid in mass comprises: trisubstituted organic phosphine,with a concentration of 1 to 10 g/L; calcium chloride, with aconcentration of 0 to 2 g/L; protease, with a concentration of 0.5 to 5g/L; and the rest is water.

Shrinkproof Treatment Method (Process) for Chlorine-Free Wool Top orWool Product

A shrinkproof treatment method for chlorine-free wool top or woolproduct is also provided in the present invention, in which the wooltop/wool product is treated with the chlorine-free descaling shrinkprooftreatment liquid of the present invention, thereby obtaining a wooltop/wool product with excellent shrinkproof properties. It should beunderstood that although the shrinkproof treatment liquid and method ofthe present invention can achieve a sufficient descaling to obtain afully descaled wool product, the method of the present invention canalso be used to produce a wool product that is not fully descaled (i.e.partially descaled).

As shown in FIG. 6, in a preferred embodiment, a continuous processingprocess of shrinkproof treatment of chlorine-free wool top and woolproduct is provided in the invention, and comprises the following steps:

1) descaling shrinkproof treatment: wool tops/wool products arearranged, and uniformly transported into one or more tanks filled withshrinkproof treatment agent and subjected to an alternate soaking androlling treatment (e.g. 3 to 10 times), wherein process conditionscomprise: pH of the shrinkproof treatment agent is 7 to 10.5,temperature is 40 to 50° C.; and total time of soaking and rolling is 1to 5 minutes; preferably, wool tops are arranged in order, and uniformlytransported into a number of tanks filled with a shrinkproof treatmentagent and subjected to an alternate soaking and rolling treatment for 3to 10 times, wherein process conditions comprise: pH of the shrinkprooftreatment agent is 7 to 10.5, temperature is 40 to 50° C.; a rollingliquid-containing rate is 60% to 150%; a process delivery speed is 3 to15 m/min (preferably 3 to 8 m/min), and total time of soaking androlling is 1 to 5 minutes;

2) water washing: the treated wool tops obtained in the previous stepare transported by rolling into one to four water tanks for multiplewashing, thereby removing residual biological enzyme activator andenzyme preparation to prevent them from continuously eroding wool;

3) inactivation of protease: the washed wool tops are quickly passedthrough a hot water tank filled with hot water having a temperature of85 to 95° C. or a solution containing 0.1 to 1 g/L of hydrogen peroxide,thereby inactivating any protease which is not completely washed out;

4) soft treatment: the inactivated wool tops are soaked in a tank filledwith a conventional wool smoothing agent or organosiliconsoftening-agent, and a common soft treatment is conducted to improvefeel of wool fabric;

5) dehydration and drying;

wherein the shrinkproof treatment agent mainly contains: trisubstitutedorganic phosphine in a concentration of 1 to 10 g/L; calcium chloride ina concentration of 0.3 to 2 g/L; protease in a concentration of 0.5 to 5g/L; and the rest is water; the trisubstituted organic phosphine is atleast one of tris(3-hydroxypropyl)phosphine,tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine andtris(4-carboxybutyl)phosphine.

In another preferred embodiment, the immersion (or soaking) and rollingoperation may be repeated for a plurality of times, for example, 3 to 10times.

In the present invention, the total time of the soaking and rollingtreatment is not particularly limited, and is usually 0.5 to 20 minutes,preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

The present invention requires only a very short total time for thesoaking/rolling operation, since the chlorine-free descaling shrinkprooftreatment agent of the present invention can descale very efficientlyand with almost no damage.

In another preferred embodiment, the chlorine-free shrinkproof treatmentprocess of the present invention is continuous, wherein the deliveryspeed in the continuous process may be from 0.5 to 20 m/min, andpreferably from 1 to 10 m/min.

In a preferred embodiment of the present invention, the processcomprises: 1) shrinkproof treatment. The wool tops are subjected to adescaling treatment using an integrated protease catalytic system. Inthe case when every wool top has no tension, the wool tops are arrangedin order, and uniformly transported with roller into an high-efficientcatalytic system composed of a protease, a water-soluble aliphatictrisubstituted organic phosphine biological enzyme activator andinorganic salt catalyst. A conventional non-ionic surfactant asauxiliary penetrant can also be added, pH is 7 to 10.5, and temperatureof the catalytic system is 40 to 50° C., when the wool tops arecompletely (soaking and exchange rate between wool fibers and thesurrounding treatment fluid can be accelerated by using a suction rolleror other equipments), and the wool tops are squeezed with rollers sothat a liquid-containing rate is 60% to 150%.

Then, they are transferred again into a catalytic system having atemperature of 40 to 50° C., and after being immersed, the wool tops aresqueezed with rollers, and this soaking and rolling treatment isrepeated. The process speed is controlled between 3 to 15 m/min(optionally 3 to 8 m/min). According to different wool branches andproduct quality requirements, in the treatment solution of the sameintegrated catalytic system and under the same treatment conditions, thetreatment is conducted for 1 to 5 minutes and for 3 to 10 times, andfinally the obtained wool tops are transported into a follow-upprocessing tank, thereby achieving continuous automation effects.

2) water washing. The treated wool tops obtained in the previous stepare transported by roller into one to four water tanks for multiplewashing, thereby removing residual biological enzyme activator andenzyme preparation to prevent them from continuously eroding wool.

3) inactivation of protease. The washed wool tops obtained in step 2)are evenly and quickly passed through a boiling water tank or a solutioncontaining 0 to 1 g/L of hydrogen peroxide, thereby inactivating anyprotease that is not completely washed out.

4) soft treatment. The inactivated wool tops are soaked in aconventional wool smoothing agent or organosilicon softening-agent (thatis, in a soft treatment tank, a general soft treatment is carried out,and the soft agent is a hydrogen-containing silicone oil, an aminosilicone oil, and a modified silicone oil or an emulsion thereof), so asto improve feel of wool fabric.

5) dehydration and drying (conventional methods can be used).

Chlorine-Free Treatment Device

A chlorine-free treatment device for use in the method of invention isalso provided in the present invention.

A typical treatment device is shown in FIG. 7. The device comprises:

a multiple padding apparatus 10, which comprises n independent,continuously arranged padding machines (not shown), and every paddingmachine comprises a soaking tank and a rolling roller, wherein thesoaking tank is used for placing a shrinkproof treatment agent forchlorine-free shrinkage treatment and the wool top or the wool productto be treated is immersed in the treatment agent; and the rolling rolleris used for rolling the soaked wool top or wool product, and the wooltop or wool product rolled by rolling rollers upstream enters into thesoaking tank and the rolling roller of the padding machine downstream inturn, thereby repeating the soaking and rolling treatment, wherein n isa positive integer of 2 to 20;

a water washing apparatus 20 for water washing the padded wool tops orwool products to form washed wool tops or wool products;

an enzyme inactivation apparatus 30 for alkaline inactivation treatmentof residual protease in the washed wool tops or wool products to form anenzyme-inactivated wool tops or wool products;

an optional soft processing apparatus 40 for soft processing theenzyme-inactivated wool tops or wool products to form a softened wooltops or wool products; and an optional dryer 50 used to dry the softenedwool tops or wool products obtained in the previous step.

In another preferred embodiment, the multiple padding apparatus, thewater washing apparatus, the enzyme inactivation apparatus, the optionalsoft processing apparatus and the optional dryer are arranged insequence.

In another preferred embodiment, one or more auxiliary padding machinesare further set between or behind every padding machine of the multiplepadding apparatus, and every auxiliary padding machines independentlycomprises an auxiliary soaking tank and an auxiliary rolling roller,wherein the auxiliary soaking tank is filled with a protease treatmentsolution containing no organic phosphine compound and/or an organicphosphine compound treatment liquid containing no protease.

In another preferred embodiment, the auxiliary soaking tank is an enzymetreatment tank.

In another preferred embodiment, the enzyme treatment bath is locatedafter the second, third, fourth or fifth padding machine.

In another preferred embodiment, n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably 3 to 15, and morepreferably 4 to 10.

In another preferred embodiment, the shape and size of every paddingmachine may be the same or different.

In another preferred embodiment, every padding machine is arranged insequence.

In another preferred embodiment, the soaking tank is filled with theshrinkproof treatment agent (or liquid) according to the first aspect ofthe present invention.

In another preferred embodiment, the soaking tank is a suction rollertank.

In another preferred embodiment, the soaking tank is independentlyequipped with or without a heating apparatus or a temperature controlapparatus.

In another preferred embodiment, every heating apparatus or everytemperature control apparatus controls the temperature in a range of 25to 80° C. by, preferably 30 to 70° C., more preferably 40 to 60° C., andmost preferably 45 to 55° C.

In another preferred embodiment, the water washing apparatus comprises mwater scrubbers, wherein m is a positive integer of 1 to 10, preferably1 to 6, and preferably 2 to 4.

In another preferred embodiment, every water scrubber is filled with asolvent of water.

In another preferred embodiment, in every water scrubber, temperature ofthe solvent water is 10-40° C., preferably 20 to 30° C.

In another preferred embodiment, in every water scrubber, pH of thesolvent water is 6.5-7.5, preferably 7±0.2.

In another preferred embodiment, the enzyme inactivation apparatus is ahigh temperature inactivation tank and/or a hydrogen peroxideinactivation tank.

In another preferred embodiment, in the enzyme inactivation apparatus,the temperature of the solvent water is from 85 to 100° C., preferablyfrom 90 to 98° C., and more preferably from 92 to 96° C.

In another preferred embodiment, the enzyme inactivation apparatus isfilled with a H₂O₂ solution.

In another preferred embodiment, in the enzyme inactivation apparatus,the concentration of the H₂O₂ in the solution is 0.01 to 50 g/L,preferably 0.05 to 30 g/L, and more preferably 0.1 to 10 g/L.

In another preferred embodiment, the soft treatment apparatus is filledwith the soft treatment agent selected from the group consisting of:wool smoothing agents, wool softening agents, or combinations thereof.

In another preferred embodiment, in the soft treatment apparatus, thesoft treatment agent has a concentration of about 1 to 50 g/L,preferably 2 to 40 g/L, and more preferably 5 to 25 g/L.

In another preferred embodiment, the wool softening agent includes anorganic silicon softening agent.

In another preferred embodiment, the organic silicon softening agent isselected from the group consisting of: silicone oil, hydrogen siliconeoil, amino silicone oil, modified silicone oil, or combinations thereof.

Chlorine-Free Wool Top/Wool Product

Shrinkproof chlorine-free wool top/wool product with little or noorganochlorine residue obtained with the chlorine-free shrinkagetreatment process of invention is also provided in the presentinvention.

As used herein, the term “ecoshine” or “ecoshine product” refers to ashrinkproof chlorine-free wool top/wool product with little or noorganochlorine residue obtained with the chlorine-free shrinkagetreatment process of the present invention.

The chlorine-free treated wool tops or wool products (i.e. ecoshineproduct) of the present invention have excellent properties including(but not limited to):

(a) a high scale layer removal rate: the scale layer removal rate ofwool surface layer of the treated wool product is from 80 to 100%,preferably from 90 to 100%, and more preferably from 95 to 100% (such asfrom 99 to 100%), when it is compared with that of the wool product tobe treated.

(b) a low shrinkage rate: the absolute value of shrinkage rate of thetreated wool product is ≦10%, preferably ≦8%, preferably ≦6%, morepreferably ≦5%, and most preferably ≦3%, when it is compared with thatof the wool product to be treated, wherein the measurement methodthereof is TWC.TM31 test method of the International Wool Bureau.

(c) high strength retention: after treated by the shrinkproof treatmentmethod, strength retention of the treated wool product is ≧80%,preferably ≧82%, and more preferably ≧84%, when it is compared with thatof the wool product to be treated.

(d) high elongation retention: after treated by the shrinkprooftreatment method, elongation retention of the treated wool product is≧70%, preferably ≧75%, and more preferably ≧80%, when it is comparedwith that of the wool product to be treated.

(e) excellent wetting and penetration performance: drip diffusion time(according to GB/T21655.1-2008) is increased from ≧10 minutes (beforetreatment) to ≦10 seconds.

Treatment Mechanism and Advantages

The present inventors provides the following mechanism for the purposeof facilitating understanding of the present invention. However, itshould be understood that the invention is not limited by thismechanism.

The present inventors have found that there are some specific structuresand substances in the scale layer of the wool surface, such as disulfidebond-containing cystine and lipids and so on, which make it difficultfor the protease to efficiently digest and decompose the high-sulfurprotein on the surface of the scale and therein. However, in thepresence of the organic phosphine compound represented by formula A ofthe present invention, by using the multiple padding process of thepresent invention, on the one hand, the structure of the scale layer onthe surface of the wool can be effectively altered, which makes thatproteins such as high-sulfur protein are more prone to be decomposed byprotease, and on the other hand, the vitality of the protease can bemaintained or enhanced, thereby achieving descaling and shrinkprooftreatment of wool with very high efficiency and high speed.

In the preferred treatment agent of the present invention, the action ofthe protease is mainly to degrade the scale on the surface of wool fiberby hydrolysis; on the one hand, the water-soluble aliphatictrisubstituted organic phosphine rapidly reduces a large number ofdisulfide bond existed in the scale and activates the reaction substrateby its unique effect on the disulfide bonds in the wool so as tofacilitate the reaction between the protease and wool macromolecule.Furthermore, it has good stabilizing effect on the activity of theprotease, and can effectively reduce the decline of protease activity inthe integrated catalytic system, while at the same time it is also ableto further activate the catalytic action of protease, resulting in arapid reaction effect. In addition, the main role of the inorganic saltcatalyst is to further activate the protease; and the main role of thesurfactant is to assist treatment solution to wet and infiltrate thesurface of wool fiber as soon as possible.

In the process of the present invention, multiple padding or repeatedpadding is also a necessary condition for the present invention toachieve a rapid process. During the process of repeated padding, rapidcontact and interaction between the protease, the activator and woolfiber surface are realized compulsively, and it is helpful to clear thereactants and hydrolyzes so as to facilitate further reaction.

Compared with the prior art, the present invention has following mainadvantages:

(1) It is environmentally friendly since no chlorine-containing organicmatter or chlorine gas is used. The present invention uses thehigh-efficiency catalytic system mainly composed of the protease and theactivator of water-soluble organic phosphine structure as a treatmentliquid to treat wool. By using a synergistic effect therefrom, one canachieve the mercerizing shrinkproof continuous processing of thechlorine-free wool tops, and no toxic and hazardous substances isproduced during the process. It solves fundamentally environmentpollution caused by the chlorinated mercerization, and is in concordwith the “ecologic textiles” concept because it does not causeenvironmental pollution.

(2) The process is simple and easy to control.

(3) High processing efficiency and rapid processing speed. Compared withthe known protease shrinkproof process, the method of invention is fast,and shrinkproof treatment of wool can be completed in 1 to 5 mins, andit can ensure its mechanical properties within the acceptable range.

(4) The anti-felting effect is long and lasting.

(5) It is suitable for large-scale production. The process of theinvention has low requirement for equipment, can be continuouslyconducted, and is conducive to realize the industrial production.

The present invention will be further illustrated below with referenceto the specific examples. It should be understood that these examplesare only to illustrate the invention but not to limit the scope of theinvention. The experimental methods with no specific conditionsdescribed in the following examples are generally performed under theconventional conditions, or according to the manufacturer'sinstructions. Unless indicated otherwise, parts and percentage arecalculated by weight.

The reagents involved in the examples are commercially available, unlessspecifically described.

The treatment liquid of the present invention is prepared by weighingthe protease, the water-soluble aliphatic trisubstituted organicphosphine compound, the inorganic salt and the surfactant according tothe amount of the main formula and using the general mass concentration(g/L) preparation method. The organic phosphine compound were purchasedfrom TianJin Littoral Orient Technology Co., Ltd.

Example 1

In the present example, the wool tops were subjected to a chlorine-freeshrinkproof treatment using a continuous process having five-multiplepadding.

Full wool tops to be treated had a specification of 70. The processcomprised the following steps:

The first tank contained a padding treatment solution. The tank had awidth of 1 m and a volume of 360 liters and was equipped with a suctionroller tank having a circumference of 1 meter (general apparatus). Thesuction roller tank had an automatic heating apparatus (generalapparatus) inside, and the tank was filled with a high efficiencycatalytic solution mainly composed of alkali protease 3 g/L andtris(3-hydroxypropyl)phosphine 3 g/L (nonionic surfactant JFC 1 g/L wasadded), and pH thereof was 9 (using disodium hydrogen phosphate andsodium dihydrogen phosphate as a pH regulator), and temperature thereofwas controlled at 50° C.

The wool tops were evenly arranged side by side on the roller anduniformly transported into the treatment liquid at a speed of 8 m/min,so that the wool tops were completely wet to ensure that the surface ofevery fiber of the wool tops was evenly and thoroughly treated. Then thewool tops were squeezed by the pressure roller to ensure that theliquid-containing rate of the wool tops was about 135%. Afterwards, thewool tops containing the enzyme fluid entered into the second treatmenttank at a speed of 8 m/min. It took 15 seconds from the time when thewool tops entered into the first tank treatment liquid to the time whenthe wool tops entered into the second tank treatment liquid.

The second tank: padding treatment solution. They are the same as thosefor the first tank.

The third tank: padding treatment solution. They are the same as thosefor the first tank.

The fourth tank: padding treatment solution. They are the same as thosefor the first tank.

The fifth tank: padding treatment solution. They are the same as thosefor the first tank. It took 15 seconds×5=75 seconds from the beginningof first tank to the end of the fifth tank.

The sixth tank: water washing. The wool tops were rolling washed byrolling, so that the reagents, enzymes and degraded products attached onthe surface of the wool fiber were cleaned. The water temperature wasroom temperature, and pH was 7.0.

The seventh tank: the second water washing. They are the same as thosefor the sixth tank.

The eighth tank: water washing at high temperature. It played a role ofenzyme inactivation, so as to prevent subsequent continuous erosion ofwool fibers. Temperature was 95° C. and time was 15 seconds.

The ninth tank: conventional soft treatment. The wool fiber weresoftened to achieve soft effect and to improve the feel. Afterwards, thewool tops were subjected to conventional dehydration and drying (forexample: drying process conditions:drying temperature was 70 to 90° C.,and drying time was 3 to 10 minutes).

The process speed was 8 m/min, and number of padding in the treatmentliquid was 5 times in total. After treated by this process, the scalestripping effect of the wool fiber was shown in FIG. 1.

The strength retention of the wool treated by this process was 85% andelongation retention thereof was 83%, compared with those of theuntreated wool.

According to the TWC.TM31 test method of International Wool Bureau, thewool treated by this process had a 5×5 A test results of −4.86%.

Chlorine content of the treated wool was measured, and no residualchlorine component (organic substance) was detected.

Example 2

In the present example, the wool tops were subjected to a chlorine-freeshrinkproof treatment using a continuous process having six-multiplepadding.

Full wool tops to be treated had a specification of 56. The processcomprised the following steps:

The first tank contained padding treatment solution. The tank had awidth of 1 m and a volume of 360 liters and was equipped with a suctionroller tank having a circumference of 1 meter. The suction roller tankhad an automatic heating apparatus inside, and the tank was filled witha high efficiency catalytic solution containing alkali protease 3 g/Land tris(3-hydroxypropyl)phosphine 3 g/L, and pH thereof was 10.5, andtemperature thereof was controlled at 50° C.

The wool tops were evenly arranged side by side on the roller anduniformly transported into the treatment liquid at a speed of 3.8 m/min,so that the wool tops were completely wet to ensure that the surface ofevery fiber of the wool tops was evenly and thoroughly treated; and thenthe wool tops were squeezed by the pressure roller to ensure that theliquid-containing rate of the wool tops was 130%. Afterwards, the wooltops containing the enzyme fluid entered into the second treatment tankat a speed of 3.8 m/min. It took 31.5 seconds from the time when thewool tops entered into the first tank treatment liquid to the time whenthe wool tops entered into the second tank treatment liquid.

The second tank: padding treatment solution. They are the same as thosefor the first tank.

The third tank: padding treatment solution. They are the same as thosefor the first tank.

The fourth tank: padding treatment solution. They are the same as thosefor the first tank.

The fifth tank: padding treatment solution. They are the same as thosefor the first tank.

The sixth tank: padding treatment solution. They are the same as thosefor the first tank. It took 31.5 seconds×6=189 seconds from thebeginning of first tank to the end of the sixth tank.

The seventh tank: water washing. The wool tops were rolling washed byrolling, so that the reagents, enzymes and degraded products attached onthe surface of the wool fiber were cleaned. The water temperature wasroom temperature, and pH was 7.0.

The eighth tank: the second water washing. They are the same as thosefor the seventh tank.

The ninth tank: water washing at high temperature. It played a role ofenzyme inactivation, so as to prevent subsequent continuous erosion ofwool fibers. Temperature was 95° C. and time was 15 seconds.

The tenth tank. The wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve softeffect and to improve the feel. Temperature of the softener solution was40° C., and pH thereof was 7.0, and time was 15 seconds. Afterwards, thewool tops were subjected to dehydrate and dry.

The process speed was 3.8 m/min, and number of padding in the treatmentliquid was 6 times in total. After treated by this process, the scalestripping effect of the wool fiber was shown in FIG. 2.

The strength retention of the wool treated by this process was 83% andelongation retention thereof was 72%, compared with those of theuntreated wool.

According to the TWC.TM31 test method of International Wool Bureau, thewool treated by this process had a 5×5 A test results of −3.82%.

Chlorine content of the treated wool was measured, and no residualchlorine component (organic substance) was detected.

Example 3

In the present example, the wool tops were subjected to a chlorine-freeshrinkproof treatment using a continuous process having five-multiplepadding.

Full wool tops to be treated had a specification of 90. The processcomprised the following steps:

The first tank contained padding treatment solution. The tank had awidth of 1 m and a volume of 360 liters and was equipped with a suctionroller tank having a circumference of 1 meter. The suction roller tankhad an automatic heating apparatus inside, and the tank was filled witha high efficiency catalytic solution composed of alkali protease 3 g/L,tris(3-carboxypropyl)phosphine 3 g/L and anhydrous calcium chloride 0.3g/L (nonionic surfactant JFC 1 g/L was further added), and pH thereofwas 8.5 (pH was adjusted with appropriate amount of sodium carbonate orsodium hydroxide solution), and temperature thereof was controlled at50° C.

The wool tops were evenly arranged side by side on the roller anduniformly transported into the treatment liquid at a speed of 3.8 m/min,so that the wool tops were completely wet to ensure that the surface ofevery fiber of the wool tops was evenly and thoroughly treated. Then thewool tops were squeezed by the pressure roller to ensure that theliquid-containing rate of the wool tops was 130%. Afterwards, the wooltops containing the enzyme fluid entered into the second treatment tankat a speed of 3.8 m/min. It took 31.5 seconds from the time when thewool tops entered into the first tank treatment liquid to the time whenthe wool tops entered into the second tank treatment liquid.

The second tank: padding treatment solution. They are the same as thosefor the first tank.

The third tank: padding treatment solution. They are the same as thosefor the first tank.

The fourth tank: padding treatment solution. They are the same as thosefor the first tank.

The fifth tank: padding treatment solution. They are the same as thosefor the first tank. It took 31.5 seconds×5=about 158 seconds from thebeginning of the first tank to the end of the fifth tank.

The sixth tank: water washing. The wool tops were rolling washed byrolling, so that the reagents, enzymes and degraded products attached onthe surface of the wool fiber were cleaned. The water temperature wasroom temperature, and pH was 7.0.

The seventh tank: the second water washing. They are the same as thosefor the sixth tank.

The eighth tank: water washing at high temperature. It played a role ofenzyme inactivation, so as to prevent subsequent continuous erosion ofwool fibers. Temperature was 95° C., and time was 15 seconds.

The ninth tank: the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve softeffect and to improve the feel. Temperature of the softener solution was40° C., and pH thereof was 6.0, and time was 15 seconds. Afterwards, thewool tops were subjected to dehydrate and dry.

The process speed was 3.8 m/min, and number of padding in the treatmentliquid was 5 times in total. After treated by this process, the scalestripping effect of the wool fiber was shown in FIG. 3.

The strength retention of the wool treated by this process was 81% andelongation retention thereof was 80%, compared with those of theuntreated wool.

According to the TWC.TM31 test method of International Wool Bureau, thewool treated by this process had a 5×5 A test results of −2.98%.

Chlorine content of the treated wool was measured, and no residualchlorine component (organic substance) was detected.

Example 4

In the present example, the wool tops were subjected to a chlorine-freeshrinkproof treatment using a continuous process having five-multiplepadding.

Full wool tops to be treated had a specification of 80. The processcomprised the following steps:

The first tank contained padding treatment solution. The tank had awidth of 1 in and a volume of 360 liters and was equipped with a suctionroller tank having a circumference of 1 meter. The suction roller tankhad an automatic heating apparatus inside, and the tank was filled witha high efficiency catalytic solution mainly composed of alkali protease3 g/L, tris(2-hydroxyethyl)phosphine 3 g/L and anhydrous calciumchloride 0.3 g/L (nonionic surfactant JFC 1 g/L was further added), andpH thereof was 7.5. Temperature was controlled at 50° C.

The wool tops were evenly arranged side by side on the roller anduniformly transported into the treatment liquid at a speed of 4.5 m/min,so that the wool tops were completely wet to ensure the surface of everyfiber of the wool tops was evenly and thoroughly treated; and then thewool tops were squeezed by the pressure roller to ensure that theliquid-containing rate of the wool tops was 130%. Afterwards, the wooltops containing the enzyme fluid entered into the second treatment tankat a speed of 4.5 m/min. It took 26.7 seconds from the time when thewool tops entered into the first tank treatment liquid to the time whenthe wool tops entered into the second tank treatment liquid.

The second tank: padding treatment solution. They are the same as thosefor the first tank.

The third tank: padding treatment solution. They are the same as thosefor the first tank.

The fourth tank: padding treatment solution. They are the same as thosefor the first tank.

The fifth tank: padding treatment solution. They are the same as thosefor the first tank. It took 26.7 seconds×5=about 134 seconds from thebeginning of the first tank to the end of the fifth tank.

The sixth tank: water washing. The wool tops were rolling washed byrolling, so that the reagents, enzymes and degraded products attached onthe surface of the wool fiber were cleaned. The water temperature wasroom temperature, and pH was 7.0.

The seventh tank: the second water washing. They are the same as thosefor the sixth tank.

The eighth tank: water washing at high temperature. It played a role ofenzyme inactivation, so as to prevent subsequent continuous erosion ofwool fibers. Temperature was 95° C., and time was 15 seconds.

The ninth tank: the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve softeffect and to improve the feel. Temperature of the softener solution was40° C., and pH was 6.0, and time was 15 seconds. Afterwards, the wooltops were subjected to dehydrate and dry.

The process speed was 4.5 m/min, and number of padding in the treatmentliquid was 5 times in total. After treated by this process, the scalestripping effect of the wool fiber was shown in FIG. 4.

The strength retention of the wool treated by this process was 82% andelongation retention thereof was 81%, compared with those of theuntreated wool.

According to the TWC.TM31 test method of International Wool Bureau, thewool treated by this process had a 5×5 A test results of −3.56%

Example 5

In the present example, the wool tops were subjected to a chlorine-freeshrinkproof treatment using a continuous process having seven-multiplepadding.

Full wool tops to be treated had a specification of 70. The processcomprised the following steps:

The first tank contained padding treatment solution. The tank had awidth of 1 m and a volume of 360 liters and was equipped with a suctionroller tank having a circumference of 1 meter. The suction roller tankhad an automatic heating apparatus inside, and the tank was filled witha high efficiency catalytic solution mainly composed of alkali protease2 g/L, tris(4-carboxybutyl)phosphine 3 g/L and anhydrous calciumchloride 0.3 g/L (optionally, nonionic surfactant JFC 1 g/L or anionicsurfactant was further added), and pH thereof was 8, and temperaturethereof was controlled at 50° C.

The wool tops were evenly arranged side by side on the roller anduniformly transported into the treatment liquid at a speed of 6 m/min,so that the wool tops were completely wet to ensure the surface of everyfiber of the wool tops was evenly and thoroughly treated. Then the wooltops were squeezed by the pressure roller to ensure that theliquid-containing rate of the wool tops was 130%. Afterwards, the wooltops containing the enzyme fluid entered into the second treatment tankat a speed of 6 m/min. It took 20 seconds from the time when the wooltops entered into the first tank treatment liquid to the time when thewool tops entered into the second tank treatment liquid.

The second tank: padding treatment solution. They are the same as thosefor the first tank.

The third tank: padding treatment solution. They are the same as thosefor the first tank.

The fourth tank: padding treatment solution. They are the same as thosefor the first tank.

The fifth tank: padding treatment solution. They are the same as thosefor the first tank.

The sixth tank: padding treatment solution. They are the same as thosefor the first tank.

The seventh tank: padding treatment solution. They are the same as thosefor the first tank. It took 20 seconds×7=140 seconds from the beginningof first tank to the end of the seventh tank.

The eighth tank: water washing. The wool tops were rolling washed byrolling, so that the reagents, enzymes and degraded products attached onthe surface of the wool fiber were cleaned. The water temperature wasroom temperature, and pH was 7.0.

The ninth tank: the second water washing. They are the same as those forthe eighth tank.

The tenth tank: water washing at high temperature. It played a role ofenzyme inactivation, so as to prevent subsequent continuous erosion ofwool fibers. Temperature was 95° C., and time was 15 seconds.

The eleventh tank: the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve softeffect and to improve the feel. Temperature of the softener solution was40° C., and pH thereof was 6.0, and time was 15 seconds. Afterwards, thewool tops were subjected to dehydrate and dry.

The process speed was 6 m/min, and number of padding in the treatmentliquid was 7 times in total. After treated by this process, the scalestripping effect of the wool fiber was shown in FIG. 5.

The strength retention of the wool treated by this process was 82% andelongation retention thereof was 80%, compared with those of theuntreated wool.

According to the TWC.TM31 test method of International Wool Bureau, thewool treated by this process had a 5×5 A test results of −3.01%.

Example 6

In the present example, the wool products were subjected to achlorine-free shrinkproof treatment using a continuous process havingfour-multiple padding.

The products to be treated were wool products (serge). Method was asfollows:

Four groups of Kroy deepim reaction tank (each group had a depth of 1.5m, a width of 1.8 m and a thickness of 0.4 m) were used and filled withthe integrated protease catalytic treatment solution for padding. Maincomponents of the treatment solution (efficient catalytic solution)comprised alkaline protease 1.8 g/L, tris(4-carboxybutyl)phosphine as abiological enzyme activator 3.0 g/L and anhydrous calcium chloride 0.3g/L (nonionic surfactant JFC 1 g/L was also optionally added), and pHthereof was 7.5, and temperature thereof was controlled at 50° C. Sergeto be treated in flat state was successively transported into the fourgroups of Kroy deepim reaction tanks and subjected a four-multiplepadding uniformly at a rate of 6 m/min for two minutes. Theliquid-containing rates among every two groups were controlled at 100%.Afterwards, water washing, inactivation, soft treatment and dryingtreatment were conducted.

After above treatment, wool products not only had good shrinkproofperformance, especially the wetting properties and permeability weresignificantly improved, but also the drip diffusion time thereof(according to GB/T21655.1-2008) was increased from ≧10 minutes (beforethe treatment) to ≦10 seconds.

Comparative Example 1 Treatment by Soaking Method

Descaling shrinkproof treatment was conducted by using a conventionalsoaking method, and the method was as follows:

Wool tops (70 branches, 20 g) were soaked into a soaking treatmentsolution for 20 minutes or 60 minutes (50° C.). After soaking treatment,it was subjected to a post-treatment (similar to that in Example 1) by aconventional method, which included water washing for three times,followed by enzyme inactivation treatment and soft treatment, and thenfollowed by dehydration and drying.

The formulation of the soaking treatment liquid was as follows: alkalineprotease (alkali protease) 3 g/L, nonionic surfactant JFC 1 g/L(pH=8.5), and the solvent was water.

The results showed that, when soaking time was 20 minutes, partial woolwas not fully descaled. When soaking time was 60 minutes, descalingeffect of the wool was basically uniform, but there were still a smallamount of wool not fully descaled. This showed that the soaking methodwas not suitable for large-scale production due to long treatment timeand non-uniform treatment effects.

Comparative Example 2 Treatment by Soaking-Steaming Method

This comparative example adopted a conventional batch type method, anddescaling shrinkproof treatment was conducted by using asoaking-steaming method. Method was as follows:

Wool tops (70 branches, 20 g) was fully soaked with a soaking treatmentsolution (50° C., liquid-containing rates of 120%) to carry out apre-soaking treatment for about 1 minute and then steamed (50° C.) for25 minutes in a steam box, and steam treatment liquid (The compositionthereof was the same as that of the soaking treatment solution) wasadded at the 5th, 10th, 15th and 20th minute. Soaking-steaming treatmenttook 26 minutes totally.

After soaking-steaming treatment, it was subjected to a post-treatment(similar to that in Example 1) by using a conventional method, whichincluded water washing for three times, followed by enzyme inactivationtreatment and soft treatment, and then followed by dehydration anddrying.

The formulation of the soaking treatment liquid was similar to that ofthe padding treatment solution in Example 1 except thattris(3-hydroxypropyl)phosphine was not contained. That is, theformulation was as follows: alkaline protease 3 g/L, nonionic surfactantJFC 1 g/L.

Result

After the above-mentioned shrinkproof treatment of the wool, corners ofthe scales on the surface of wool were substantially completely removed.But its uniformity was poor, in which the scales on the surface of thefiner wool were very vague while the scale layer of the thicker wool wascut very thin, indicating that this treatment process had betterstripping effect for scales of fine wool than that of coarse wool.

After treatment, the fiber strength was 10.34 cN, the strength retentionrate was 83.25%, the elongation rate was 32.30%, and the elongationretention rate was 64.77%. This indicated that the wool treated by thisprocess could meet the shrinkproof requirement, and the loss of rupturestrength was in the acceptable range, but the elongation loss wasrelatively high.

In addition, the entire soaking-steaming treatment took up to 26minutes, but the treatment effect thereof was much worse than that inany of Examples 1-5. In contrast, the total time for multiple padding inExamples 1-5 of the present invention was very low (≦5 minutes, morepreferably ≦3 minutes), and the descaling effect was more uniform, andthe shrinkproof properties was more excellent.

The present invention is characterized in that a chlorine-free and rapidcontinuous processing is provided to completely substitute chlorinationshrinkproof method so as to improve the shortcomings when proteasebiological treatment process is used alone. It also improves theprotease biological treatment method, and finally achieves the goal ofthe optimal treatment effect and improves the quality of the whole woolproduct.

All literatures mentioned in the present invention are incorporated byreference herein, as though individually incorporated by reference.Additionally, it should be understood that after reading the aboveteaching, many variations and modifications may be made by the skilledin the art, and these equivalents also fall within the scope as definedby the appended claims.

1.-18. (canceled)
 19. A shrinkproof treatment method for chlorine-freewool tops or wool products, which comprises the following steps: (a)providing chlorine-free wool tops or wool products to be treated, and ashrinkproof treatment agent for chlorine-free wool tops or woolproducts; (b) padding the chlorine-free wool tops or wool products to betreated with the shrinkproof treatment agent for n times, therebyobtaining padded wool products, wherein n is a positive integer of 2 to20; (c) water washing the padded chlorine-free wool tops or woolproducts, thereby obtaining water washed chlorine-free wool tops or woolproducts; (d) conducting an enzyme inactivation treatment of the waterwashed chlorine-free wool tops or wool products, thereby obtainingshrinkproof treated chlorine-free wool tops or wool products.
 20. Themethod according to claim 1, wherein total time T of the paddingtreatment of step (b) is ≦15 minutes.
 21. The method according to claim1, wherein n is a positive integer of 3 to
 15. 22. The method accordingto claim 1, wherein the shrinkproof treatment agent comprises: (a) anoptional solvent; (b) a protease; and (c) an organic phosphine compoundrepresented by formula A; and an optional inorganic salt;P—(X)₃  A wherein each X is independently selected from the groupconsisting of substituted or unsubstituted C₁-C₁₀ hydrocarbyl, whereinthe term “substituted” refers to one or more substituents selected fromthe group consisting of —OH, —COOH (carboxy), C₂-C₈ ester group, —SH,—CN, C₁-C₃ alkyl, C₁-C₃ alkoxy; and at least one X is a substitutedC₁-C₁₀ hydrocarbyl having a —OH or COOH substituent; the weight ratio ofthe protease to the organic phosphine compound is (0.2 to 10): (0.5 to20); and the protease in the shrinkproof treatment agent is selectedfrom the group consisting of a neutral protease, an alkaline protease,and combinations thereof.
 23. The method according to claim 22, whereinthe organic phosphine compound has the following structure formula:P—(R₁-R₂)₃  I wherein, R₁ is substituted or unsubstituted C₂-C₈alkylene; and/or R₂ is selected from the group consisting of —OH, —COOH,C₂-C₈ ester group, alkali metal, and alkaline earth metal.
 24. Themethod according to claim 22, wherein the organic phosphine compound isselected from the group consisting of tris(3-hydroxypropyl)phosphine,tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine,tris(4-carboxybutyl)phosphine, and combinations thereof.
 25. Ashrinkproof treatment device for chlorine-free wool tops or woolproducts, which comprises: a multiple padding apparatus which comprisesn independent, continuously arranged padding machines, and every paddingmachine comprises a soaking tank and a rolling roller, wherein thesoaking tank is used for placing a shrinkproof treatment agent forchlorine-free shrinkage treatment and the wool tops or the wool productsto be treated are immersed in the treatment agent; and the rollingroller is used for rolling soaked wool tops or wool products, and thewool tops or wool products rolled by a rolling roller upstream enterinto the soaking tank and the rolling roller of the padding machinedownstream in turn, thereby repeating the soaking and rolling treatment,wherein n is a positive integer of 2 to 20; a water washing apparatusfor water washing the padded wool tops or wool products to form washedwool tops or wool products; an enzyme inactivation apparatus foralkaline inactivation treatment of residual protease in the washed wooltops or wool products to form an enzyme-inactivated wool tops or woolproducts; an optional soft processing apparatus for soft processing theenzyme-inactivated wool tops or wool products to form a softened wooltops or wool products; and an optional dryer used to dry the softenedwool tops or wool products obtained in the previous step.
 26. Theshrinkproof treatment device according to claim 25, wherein one or moreauxiliary padding machines are further set between or behind everypadding machine of the multiple padding apparatus, and every auxiliarypadding machines independently comprises an auxiliary soaking tank andan auxiliary rolling roller, wherein the auxiliary soaking tank isfilled with a protease treatment solution containing no organicphosphine compound and/or an organic phosphine compound treatment liquidcontaining no protease.
 27. A shrinkproof chlorine-free wool productwherein there is no residual organic chlorine in the wool product andthe chlorine-free wool product is chlorine-free treated using theshrinkproof treatment device according to claim
 25. 28. A shrinkproofchlorine-free wool product wherein there is no residual organic chlorinein the wool product and the chlorine-free wool product is chlorine-freetreated using the method according to claim
 19. 29. The shrinkproofchlorine-free wool product according to claim 28, wherein thechlorine-free wool product has four or five characteristics selectedfrom the group consisting of: (a) after treated by the shrinkprooftreatment method, scale layer removal rate of wool surface layer of thetreated chlorine-free wool product is 80 to 100% compared with that ofthe wool product to be treated; (b) after treated by the shrinkprooftreatment method, the absolute value of shrinkage rate of the treatedchlorine-free wool product is ≦5%, when it is compared with that of thewool product to be treated, wherein measurement method thereof isTWC.TM31 test method of the International Wool Bureau; (c) after treatedby the shrinkproof treatment method, strength retention of the treatedchlorine-free wool product is ≧80% compared with that of the woolproduct to be treated; (d) after treated by the shrinkproof treatmentmethod, elongation retention of the treated chlorine-free wool productis ≧75% compared with that of the wool product to be treated; (e) dripdiffusion time of the treated chlorine-free wool product is ≦15 s. 30.An article, wherein the article comprises the wool product according toclaim 28 or is made of the wool product according to claim
 28. 31. Ashrinkproof treatment agent for chlorine-free wool tops and woolproducts, wherein its main components comprise a protease, awater-soluble aliphatic trisubstituted organic phosphine compound, andan inorganic salt; and the water-soluble aliphatic trisubstitutedorganic phosphine has a structure of P—(R—S)₃, wherein R is hydrocarbylcontaining 1 to 6 carbon, S is hydroxyl or carboxyl and derivativesthereof; and mass concentration thereof is 1 to 10 g/L; the inorganicsalt is calcium chloride, and concentration thereof is 0 to 2 g/L. 32.The shrinkproof treatment agent according to claim 31, wherein thetrisubstituted organic phosphine is at least one oftris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine,tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine.
 33. Acontinuous processing process for shrinkproof treatment of chlorine-freewool tops and wool products, wherein it comprises following steps: 1)shrinkproof treatment: wool tops and wool products are arranged, anduniformly transported with a roller into a number of tanks filled withshrinkproof treatment agent and subjected to an alternate soaking androlling treatment for 3 to 10 times, wherein process conditionscomprising: pH of the shrinkproof treatment agent is 7 to 10.5,temperature is 40 to 50° C.; a rolling liquid-containing rate is 60% to150%; process delivery speed is 3 to 15 m/min, and total time of soakingand rolling is 1 to 5 minutes; 2) water washing: the treated wool topsobtained in the previous step are transported by rolling into one tofour water tanks for multiple washing, thereby removing residualbiological enzyme activator and enzyme preparation to prevent them fromcontinuously eroding wool; 3) inactivation of protease: the washed wooltops are evenly and quickly passed through a hot water tank filled withhot water having a temperature of 85 to 95° C. or a solution containing0 to 1 g/L of hydrogen peroxide, thereby inactivating any protease whichis not completely washed out; 4) soft treatment: the inactivated wooltops are soaked into a tank filled with a conventional wool smoothingagent or organosilicon softening-agent, and a common soft treatment isconducted to improve feel of wool fabric; 5) dehydration and drying;wherein the shrinkproof treatment agent mainly contains: trisubstitutedorganic phosphine, with a concentration of 1 to 10 g/L; calciumchloride, with a concentration of 0.3 to 2 g/L; protease, with aconcentration of 0.5 to 5 g/L; and the rest is water; and thetrisubstituted organic phosphine is at least one oftris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine,tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine.
 34. Theprocess according to claim 33, wherein the soaking and rolling treatmentor padding treatment is repeated for 3 to 10 times; total time for thepadding treatment is between 1 and 5 minutes; and process delivery speedis 3 to 8 m/min.
 35. The process according to claim 33, wherein the wooltops are wool or cashmere of 56 to 100 branches.